Home Physical Sciences Synthesis and structural characterization of a dimeric N,N-dimethylformamide solvate of isobutyltin(IV) dichloride hydroxide, [iBuSnCl2(OH)(DMF)]2
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Synthesis and structural characterization of a dimeric N,N-dimethylformamide solvate of isobutyltin(IV) dichloride hydroxide, [iBuSnCl2(OH)(DMF)]2

  • Hans Reuter EMAIL logo and Fei Ye
Published/Copyright: August 23, 2013
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Main Group Metal Chemistry
From the journal Main Group Metal Chemistry Volume 36 Issue 5-6

Abstract

The title compound, isobutyltin(IV) dichloride hydroxide N,N-dimethylformamide solvate {[iBuSnCl2(OH)(DMF)]2}, an accidental side product from the reaction of isobutyltin(IV) trichloride with moisture in N,N-dimethylformamide, exhibits structural features similar to those of the corresponding hydrates of monoorganotin(IV) dihalide hydroxides characterized by a central four-membered rhombic Sn-O ring and tin atoms with a distorted octahedral coordination.

Keywords: crystal structure; organotin compounds; synthesis

Monoorganotin(IV) dihalide hydroxides, RSnHal2(OH) (1) are the first hydrolysis products of monoorganotin(IV) halides, RSnHal3. Until now, these intermediates could only be isolated as hydrates, 1·H2O. X-ray diffraction studies [R=isopropyl, isobutyl (Puff and Reuter, 1989); R=n-butyl (Holmes et al., 1988); R=ethyl (Lecomte et al., 1976); R=trans-myrtanyl (Beckmann et al., 2009); R=methyl (Johnson and Knobler, 1994); R=n-butyl (Chen, 1994)] have shown that these hydrates are dimeric (Scheme 1) with a central four-membered tin-oxygen ring and distorted octahedrally coordinated tin atoms.

Scheme 1
Scheme 1

By chance, we were able to isolate the first unhydrated dihalide hydroxide of composition [iBuSnCl2(OH)(DMF)]2 (1·DMF) exhibiting similar structural features as the hydrates but with N,N-dimethylformamide (DMF), in place of water. The title compound was obtained in the course of a systematic study on the coordination behavior of isobutyltin(IV) trichloride (iBuSnCl3) during the preparation of the corresponding coordination compound with DMF. After prolonged standing at atmosphere, large colorless, needle-like single crystals of 1·DMF were formed probably because of the reaction of iBuSnCl3 with moisture.

1·DMF crystallizes in the non-centrosymmetric monoclinic space group P21 as a racemic twin with two formula units [iBuSnCl2(OH)(DMF)]2 in the asymmetric unit (Figure 1). The molecular structure of both molecules comprises a non-centrosymmetric dimer with a central four-membered tin-oxygen ring. In the hydrates mentioned above, the dimers are centrosymmetric. Despite the lack of a center of symmetry, the tin-oxygen rings are nearly planar and exhibit the typical rhombic shape of four-membered tin-oxygen rings with large angles at oxygen [Sn1-O1-Sn2=108.1(1)°; Sn1-O2-Sn2=108.2(1)°; Sn3-O3-Sn4=109.5(1)°; Sn3-O4-Sn4=109.5(1)°] and small ones at tin [O1-Sn1-O2=71.6(1)°; O1-Sn2-O2=72.1(1)°; O3-Sn3-O4=70.7(1)°, O3-Sn4-O4=70.3(1)°]. Moreover, Sn-O bond lengths are unequal [d(Sn1-O1)=2.068(3) Å, d(Sn2-O1)=2.163(3) Å; d(Sn2-O2)=2.058(3) Å, d(Sn1-O2)=2.173(3) Å], with the longer ones in trans position (Buslaev et al., 1989) to the organic groups. Isobutyl groups are well ordered with normal thermal displacement parameters giving rise to typical C-C bond lengths in the range 1.509(6)–1.544(7) with a mean value of 1.527(10) Å.

Figure 1 Molecular structure of [iBuSnCl2(OH)(DMF)]2 (molecule 1) showing the atomic numbering scheme used, with the exception of the hydrogen atoms, which are shown as spheres of arbitrary radius. All other atoms are shown as thermal displacement ellipsoids representing the 50% probability level of the corresponding atoms.
Figure 1

Molecular structure of [iBuSnCl2(OH)(DMF)]2 (molecule 1) showing the atomic numbering scheme used, with the exception of the hydrogen atoms, which are shown as spheres of arbitrary radius. All other atoms are shown as thermal displacement ellipsoids representing the 50% probability level of the corresponding atoms.

Sn-Cl bond lengths are very similar [d(Sn1-Cl11)=2.449(1) Å, d(Sn1-Cl12)=2.436(1) Å, d(Sn2-Cl21)=2.446(1) Å, d(Sn2-Cl22)=2.448(1) Å; d(Sn3-Cl31=2.451(1) Å, d(Sn3-Cl32)=2.464(1) Å, d(Sn4-Cl41)=2.457(1) Å; d(Sn4-Cl42)=2.441(1), mean value 2.449(9) Å], but somewhat longer than in SnCl4 [mean value: 2.279(3) A (Reuter and Pawlak, 1999)]. The four different DMF molecules are almost planar with characteristic bond lengths and angles [d(C-O)=1.257(4), d(C-N)=1.312(3), d(N-CH3)=1.457(8), O-C-N=123.0(10)°]. In summary, the octahedral coordination sphere of all tin atoms is distorted.

In the infrared (IR) spectrum, the C-O stretching vibration is shifted by 17 cm-1 to lower energy, indicating a weakening of the C-O double bond as a result of complex formation.

Both molecules of the asymmetric unit are linked via four O-H···Cl hydrogen bridges [d(O1···Cl411)=3.164(3) Å, O1-H1···Cl411=165.1°; d(O2···Cl32)=3.193(3) Å, O2-H2···Cl32=167.0°; d(O3···Cl22)=3.258(3) Å, O3-H3···Cl22=171.2°; d(O4···Cl122)=3.385(3) Å, O3-H3···Cl122=174.3°; symmetry codes: (1) x, y, z-1; (2) x, y, z+1], resulting in the formation of strands parallel to the c axis. Localization of the hydrogen atoms of the hydroxyl groups reveals the pyramidal coordination of the oxygen atoms of the hydroxyl groups to the hydrogen atom and two tin atoms (Figure 2).

Figure 2 Ball-and-stick model of the hydrogen bonding system in the crystal structure of 1·DMF.Isobutyl groups and DMF molecules are omitted for clarity, -OH Cl hydrogen bonds are indicated by green broken sticks; symmetry code: (1) x, y, −1+z.
Figure 2

Ball-and-stick model of the hydrogen bonding system in the crystal structure of 1·DMF.

Isobutyl groups and DMF molecules are omitted for clarity, -OH Cl hydrogen bonds are indicated by green broken sticks; symmetry code: (1) x, y, −1+z.

Experimental

iBuSnCl3 (0.56 g, 2 mmol) (Neumann and Burkhardt, 1963) was mixed with about 0.60 g (8 mmol, large excess with respect to a 1:2 complex) of N,N-dimethylformamide (Sigma-Aldrich) on a Petri dish. Excess solvent was allowed to evaporate slowly within a hood. No special attention was made to exclude moisture. After 2 weeks, large, needle like, colorless single crystals of the title compound were formed within the remaining liquid. Crystals were separated by filtration and dried in air (yield 0.24 g). Elemental analysis (calc./found) was performed with a VarioMicrocube (Elementar Analysensysteme GmbH, Hanau, Germany): C 24.96%/25.06%; H 5.09%/4.89%; N 4.16%/4.02%.

IR spectra

Attentuated total reflectance Fourier transform IR spectroscopy (cm-1) was recorded using a Bruker Vertex 70 (Bruker AXS GmbH, Karlsruhe, Germany): 3391 w, br, ν(O-H); 2950 w; 1641 vs, ν(C=O); 1489 w; 1430 m; 1365 s; 1245 m, 1158 w, 1120 m; 1088 w; 1056 w, 980 m, br; 740 m; 686 s; 610 w; 496 m.

X-ray structure determination

A suitable single crystal was mounted on a 50-µm MicroMesh MiTeGen Micromount™ using FROMBLIN Y perfluoropolyether (LVAC 16/6, Aldrich). X-ray measurements were performed on a Bruker APEX-II CCD diffractometer (Bruker AXS GmbH, Karlsruhe, Germany) at 100 K using graphite-monochromated Mo-Kα (0.7107 Å) radiation. Data were collected, reduced, and corrected for absorption using multiscan technique (Bruker, 2008). The structure was solved by direct methods and refined using full-matrix least-squares refinements on F2. All H atoms were found in difference Fourier synthesis; those of the organic groups and the DMF molecules were placed in geometrical position. H atoms of the hydroxyl groups were refined with respect to a common O-H distance of 0.96 Å before they were fixed and allowed to ride on the corresponding oxygen atoms with a common isotropic displacement factor (Sheldrick, 2008). Figures were drawn using DIAMOND (Brandenburg, 2006).

C14H34Cl4N2O4Sn2, 673.61 g/mol, T=100 K, monoclinic, P21 (No. 4), a=11.0351(3) Å, b=18.7005(4) Å, c=12.7410(3) Å, β=106.107(1)°, V=2526.1(1) Å3, Z=4, dcalc=1.771 g/cm3, µ(Mo-Kα)=2.420 mm-1, F(000)=1328, 2max=56°, reflcol=55,897, reflunique=11,527, Rint=0.0707, Rσ=0.0581, completeness=99.8%, absorption correction=semi-empirical from equivalents, Tmax/Tmin=0.9010/0.5729, data/restraints/parameters=11527/1/496, R1/wR2[I>2σ(I)]=3.11%/5.57%, R1/wR2[all data]=3.97%/5.89%, absolute structure parameter=0.576(16), twin refinement, extinction coefficient=0.00091(7), largest diff. peak/hole=0.654/-0.565 e/Å3. Crystallographic data of the title compound have been deposited with the Cambridge Crystallographic Data Centre, CCDC number 946286. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).

Corresponding author: Hans Reuter, Institut für Chemie neuer Materialien, Universität Osnabrück, D-49069 Osnabrück, Germany, e-mail:

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Received: 2013-7-12
Accepted: 2013-7-25
Published Online: 2013-08-23
Published in Print: 2013-12-01

©2013 by Walter de Gruyter Berlin Boston

This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

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https://doi.org/10.1515/mgmc-2013-0037
Keywords for this article
crystal structure; organotin compounds; synthesis
Creative Commons
BY-NC-ND 3.0

Articles in the same Issue

  1. Masthead
  2. Masthead
  3. Review
  4. Structural characterization of heterometallic platinum complexes with non-transition metals. Part V: Heterooligo- and heteropolynuclear complexes
  5. Research Articles
  6. {Sn10Si(SiMe3)2[Si(SiMe3)3]4}2-: cluster enlargement via degradation of labile ligands
  7. Unusual reaction pathways of gallium(III) silylamide complexes
  8. Molecular structures of pyridinethiolato complexes of Sn(II), Sn(IV), Ge(IV), and Si(IV)
  9. Arylphosphonic acid esters as bridging ligands in coordination polymers of bismuth
  10. Synthesis of germanium dioxide nanoparticles in benzyl alcohols – a comparison
  11. X-ray crystal structures of [(Cy2NH2)]3[C6H3(CO2)3]·4H2O and [i-Bu2NH2][(Me3 SnO2C)2C6H3CO2]
  12. Crystal and molecular structure of bis(di-n-propylammonium) dioxalatodiphenylstannate, [n-Pr2NH2]2[(C2O4)2SnPh2]
  13. Short Communication
  14. Synthesis and structural characterization of a dimeric N,N-dimethylformamide solvate of isobutyltin(IV) dichloride hydroxide, [iBuSnCl2(OH)(DMF)]2
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